Dialiphaticaminoalkylcardanol



Patented Nov. 29, 1949 DIALIPHATICAMINOALKYLCARDANOL Anthony J. Revukas, Cranford, N. J., assignor to Tide Water Associated Oil Company, Bayonne, N. J a corporation of Delaware No Drawing. Application November 19, 1947, Serial No. 787,037

14 Claims. (Cl. 260-570.9)

This application is a continuation-in-part of my application, Serial No. 714,663, filed December 6, 1946, now abandoned.

In board aspect, the present invention relates to a novel group of chemical compounds that consist of dialiphatic aminoalkyl cardanols characterized by having a sum of more than six carbon atoms in the dialiphatic grouping and, preferably, a total of about to about carbon atoms. Illustrative of the type of compounds embodied by the present invention are diamylaminomethylcardanol, di-2-ethylhexylaminomethylcardanol, dilaurylaminomethylcardanol, and the like.

In my practice of the present invention, the dialiphatic aminoalkylcardanols are prepared by condensation reaction between cardanol, a secondary aliphatic amine containing more than six carbon atoms, and an aldehyde, as for example an aliphatic aldehyde, such as formaldehyde, acetaldehyde, and homologs thereof, the transformation consisting in the replacement of a reactive hydrogen atom of cardanol by a dialiphatic aminoalkyl grouping. Thus, when formaldehyde is employed, a dialiphatic aminomethylcardanol is formed; when use in made of a higher aldehyde, such as acetaldehyde, propionaldehyde, and the like, the resulting products contain an alkyl substituent for a hydrogen atom of the methylene group connecting the nitrogen atom and the cardanol nucleous. Illustrative of such a method is the procedure as set forth hereinafter which, though relating to preparation of diamylaminomethylcardanol, may suitably be employed for preparing the novel group of compounds embodied herein.

Preparation procedure Cardanol, obtained as a heart out (boiling point of about 180 to 230 C.) by distillation of a commercial grade of cardanol at 2 mm. pressure, and diamylamine are charged into a one liter, 3-neck round-bottom flask equipped with a thermometer, a vacuum type stirrer, a dropping funnel, and a reflux condenser. The cardanol and amine are charged in a ratio of one mole of cardanol to at least one mole, e. g., about 1.2 moles, of the amine.

The cardanol-diamylamine solution is stirred vigorously and chilled to below about 20 C., e. g., about 10 C. A suitable aldehyde, as for example formaldehyde, as in the form of a 32-37% aqueous solution, is added slowly, e. g., dropwise, to the flask while the charge is maintained at a temperature not in excess of about 20 C. until at controlled so as to prevent the temperature of the charge from increasing to more than about 20 C., as a temperature rise to above about 20 C. before formaldehyde addition is completed has been found to be undesirable from the view-point of inducing undesirable side reactions to take place. When all of the formaldehyde has been added, the charge is stirred at about 20 C. for about one hour. The formaldehyde-containing mixture may be allowed to stand and react at ordinary room temperatures, or, preferably, the mixture is heated at or below the boiling point of the mixture, e. g., under reflux at about 92 C. for about four hours, to expedite the desired condensation reaction whereby the cardanol is converted to the diamylaminomethylcardanol, Any unreacted diamylamine and formaldehyde, and water are removed by suitable means, preferably by distillation at a pressure of about 10 mm. The distillation is carried out by using a temperature high enough to distill off the undesired components but below the temperature at which polymerization and/or decomposition of the dialiphaticaminoalkylcardanol tends to occur. In preparation of diamylaminomethylcardanol, the distillation to remove undesirable byproducts is conducted at 10 mm. pressure and the temperature of the charge raised gradually to about C. to provide thorough stripping. As polymerization and decomposition of the desired product (diamylaminomethylcardanol) tends to set in at about C., the temperature in the reaction vessel is preferably not allowed to exceed about 145 C. The residue is then cooled to about 60 C. and filtered employing a filter aid, e. g., Celite. Diamylaminomethylcardanol, obtained as the desired reaction product, is a yellow-to-brown oily liquid of relatively high purity. The yield thereof, prepared as aforesaid, corresponds to about 98 to 100% of theory. Diamylaminomethylcardanol was found to have the following analysis and properties.

Analysis Nitrogen: Per cent Theory 2.97 Found 2.61; 2.64; 2.82; 2.78; 2.69 Hydroxylf Theory 3.62 Found 3.74; 3.39; 3.58; 3.78

Properties Density (20 C.) 0.9124 Burn (Cleveland Open Cup F.) 410 Flash (Cleveland Open Cup F.) 380 Viscosity at 100 F. (centistokes) 50.0 Color (A. S. T. M.) 4% Carbon 'residuepercent 2.30 Refractive index N 1.5009 Molar refraction:

Theory 150.53 Found 152.31

In preparing dialiphaticaminoalkylcardanols in accordance with the present invention, cardanol is condensed with at least one molecular equivalent each of the aldehyde and the dialiphatic amine. However, in order to provide for substantially complete utilization of the cardanol, it is preferable to employ a reaction mixture containing an amount of the amine and aldehyde in excess of molecular equivalents with cardanol. For example, in a preferred embodiment of the present invention, I employ a reaction charge comprising cardanol, the dialiphatic amine, and the aldehyde in proportions of one mole of cardanol to about 1.2 moles of the amine and about 1.5 moles of aldehyde. Use of the amine and aldehyde in such preferred concentrations, in pro- -viding for substantially complete conversion of cardanol to dialiphatic emincalkylcardanol, does not deleteriously afiect the desired product of reaction, as, during the preparation, unreacted amine and aldehyde, and water formed by the reaction, or otherwise present, are removed. by the distillation. On the other hand, if the reaction is conducted under conditions whereby a substantial amount of cardanol is not converted, use of distillation is unsuitable for separation of the dialiphaticaminoalkylcardanol in substantially pure form.

In further alkylcardanols, as embodied herein, the following compounds were prepared having the properties set forth. In each case, the procedure employed for preparation was similar to that set forth hereinbefo-re for preparation of diamylaminomethylcardanol. This is, properties were in the ratio of one mole of cardanol to 1.2 moles of the amine and 3-5 moles .of aldehyde, and the temperature of the charge was maintained at below about 20 C. during aldehyde addition. In the preparation of di-2-ethylhexylaminornethylcardanol. separation thereof from the reacted mixture was by distillation at 179 C. at 11 mm. pressure, di-n-butylaminomethylcarclanol Was recovered by disstillation at 130 C. at mm. pressure, and dilaurylaminomethylcardanol at 125 C. at 10 mm.

The dialiphatic aminoalkylcardanols embodied reactant illustration of dialiphaticaminoherein are, as far as I am aware, novel compounds that find a number of uses hitherto not generally characteristic of or anticipated for such a class of compounds. For example, these novel compounds have been found to possess highly eiiective demulsiiying properties for oil-water emulsions. Additionally, and of considerable practical utility is the discovery that these novel compounds have an unexpected and high degree of eiiectiveness for reducing the tendency of polymeric esters of the acrylic series to induce emulsification of an oil over and above any tendency, if any, of the oil itself to emulsify. Hence, the novel compounds as embodied 29 herein find utility as demulsifying agents for emulsions of oil with water, particularly mineral oils, and as addition agents for oil compositions containing polymeric esters of the acrylic series to decrease the tendency of the polymers to induce emulsification of the oil. In my aforesaid application, Serial No. 714,663, data has been set forth showing the highly effective demulsification properties resulting from use of diamylaminovmethylcardanol as a demulsifier for oils emulsified with either salt or distilled water and tested in accordance with the method set forth therein as procdure A. Briefly, the test method comprises preparation of a mixture of 40 parts by volume of the oil composition with 40 parts of either distilled or salt water, heating the mixture to 130 F., stirring the mixture for five minutes at 1500 revolutions per minute at 130 F. to emulsiiy the mixture, and maintaining the resulting composition at 130 F. and observing the amount of emulsion, in milliliters, present at five minute intervals over a period of minutes. Employing the same test procedure, the following tabulation clearly shows the highly effective demulsifying characteristics provided by use of dialiphaticaminoalkylcardanols having a sum of more than six carbon atoms in the dialiphatic grouping, i. e., the compounds as embodied herein. The presence of such a relatively high number of carbon atoms in the dialiphatic grouping is of considerable importance, especially when the compounds are employed for demulsiiying oilwater emulsions, as is evidenced b the data included in the following tabulation showing the highly inefiective results obtained when using compounds of the same class, homologous with respect to the dialiphatic grouping, but which contain a lower number of carbon atoms in the dialiphatic grouping. As shown, whereas compounds as embodied herein functioned satisfactorily as demulsiiiers, use of dimethylaminomethycardanol and diethylaminomethylcardanol not only failed to perform as clemulsifiers but, on the contrary, actually enhanced emulsification of oil-water emulsions:

Results employing test procedure A h h ig? Test Composition (equal parts by volume) Per gg gg gig ig gggf amc 30 min. 60 min. reading reading BASE EMULSIONS ml. ml. 1. turliinte; grade lubricating oil and aqueous salt None 14 12 so u ion. 2 turbine grade lubricating oil and distilled None 9 8 water.

acaaova Results employing O h test procedure A Test Composition (equal parts by volume) Per gg gg g ik g gggf 30 min. 60 min. reading reading BASE EMULSIONS PLUS DIALIPHATICAMINOMETHYLCARDANOLS CONTAINING MORE THAN SIX CARBON ATOMS IN THE DIALIPHATIC GROUPING same as test 110. 1 same as test no. 2

0.05 (iliiamylaminomethylcardanol 2 ii 0.05 dibutylaminomethylcardanol 3 1 0.05 di-Z-ethylhexylaminomethylcardanol Oomple e resolution in 14 minu es.

same as test no. 2

BASE EMULSIONS PLUS DIALIPHATICAMINOMETHYLCARDANOLS THAT DO NOT THAN SIX CARBON ATOMS IN THE DIALIPHATIC GROUPING CONTAIN MORE same as test no. 1. same as test no. 2 same as test no. 1 same as test no. 2.

containing said aldehyde, heating said aldehydecontaining mixture to a temperature above 20 C., but below the boiling point of said mixture, to expedite reaction thereof and convert the cardanol therein to dialiphaticaminoalkylcardanol, and separating said dialiphaticaminoalkylcardanol from said mixture.

9. A method for preparation of dialiphaticaminoalkylcardanols which comprises preparing a solution containing cardanol and a secondary Results employing test procedure A Test Per Cent by weight of dialiphatic No, Test composltwn (equal parts by volume) aminomethylcardanol 30 min. 60 min. reading reading 12 turbine grade lubricating oil and salt water None 4 2 13.-.- same as test no. 12 0.05 Diisopropylammomethylcardan 7 4 14...- 0.05 Dilaurylamiuomethylcardanol Complete resolution in 12 minutes Although the present invention has been described in conjunction with certain preferred embodiments thereof, those skilled in the art will readily recognize that variation and modifications can be made. Such variations and modifications are to be considered to be within the purview of the specification and the scope of the appended claims.

I claim:

1. A dialiphaticaminoalkylcardanol containing a sum of more than six carbon atoms in the dialiphatic grouping.

2. A dialiphaticaminoalkylcardanol containing a sum of ten to forty carbon atoms in the dialiphatic grouping.

3. A dialkylaminomethylcardanol containing a sum of from more than six and up to forty carbon atoms in the dialkyl grouping.

4. Di-2-ethylhexylaminomethylcardanol.

5. Diamylaminomethyl cardanol.

6. Dilaurylaminomethylcardanol.

7. Di-n-butylaminomethyl cardanol.

8. A method for preparing dialiphaticaminoalkylcardanols which comprises preparing a solution of cardanol with a secondary aliphatic amine containing more than six carbon atoms in the dialiphatic grouping in a ratio of one mole of cardanol to at least one mole of said amine, adding to said solution an aldehyde in an amount at least equal to a mole equivalent with said cardanol while maintaining said solution at a temperature not exceeding about 20 C. until said aliphatic amine in a ratio of one mole of cardanol to at least one mole of amine, said amine being characterized by containing more than six carbon atoms, adding an aliphatic aldehyde to said solution in an amount at least equal to a mole equivalent with said cardanol to form a mixture containing said aldehyde, said solution being maintained at a temperature not in excess of about 20 C. until said aldehyde addition is completed, heating said aldehyde-containing mixture to a temperature above 20 0., but below the boiling point of said mixture, to convert substantially all of the cardanol to dialiphaticaminoalkylcardanol to provide a mixture containing dialiphaticaminoalkylcardanol, and separating dialiphaticaminoalkylcardanol in substantially pure form from said mixture.

10. A method for preparing dialiphaticaminoalkylcardanols in high yields and in substantially pure form which comprises (a) preparing a solution containing a ratio of one mole of cardanol to at least one mole of a secondary aliphatic amine having a sum of more than six carbon atoms (b) adding to said solution an amount of an aldehyde at least equal to a mole equivalent with said cardanol to provide an aldehyde containing mixture, said solution being maintained at a temperature not exceeding about 20 C. until said aldehyde addition is completed (0) heating said aldehyde-containing mixture to a temperature above 20 C., but below the boiling point of said mixture, to convert substantially all of said aldehyde addition is completed to form a mixture cardanol to dialiphaticaminoalkylcardanol to provide taining mixture, ((1) and recovering dialiphaticaminoalkylcardanol as a residue from said mixture by subjecting said mixture to distillation at a temperature sufficient to remove unreacted materials and reaction byproducts but below the temperature at which decomposition and polymerization of the dialiphaticaminoalkylcardanol tends to occur.

11. A method for preparing a dialiphaticaminoalkylcardanol which comprises (a) preparing a solution containing a ratio of one mol= of cardanol to at least one mole of a secondary aliphatic amine having a sum of more than six carbon at s, (b) maintaining said solution at a temperature not in excess of about 2S C. while adding thereto an aldehyde in an amount at least equal to one mole equivalent with said cardanol, said aldehyde being added at a rate insufiicient to increase the temperature of said solution to more than about 29 C., to provide an aldehyde-co taining mixture heating said aldehyde-contain ng mixture to above 20 C., but below the boiling point of said mixture, to expedite reaction thereof and convert substantially all of said cardanol to dialiphaticaminoalkylcardanol to provide a dialiphaticaminoalkylcardanol-containing mixture, ((2) distilling said dialiphaticarninoalkylcardanol-containing mixture at a temperature below that at which the dialiphaticarninoalkylcardanol tends to decompose but at a temperature effective to remove unreacted components and reaction by-products contained such mixture, and (e) recovering dialiphaticaminoalkylcardanoi as the residue from said distillation.

12. A method for preparing diamylarninomethylcardanol in high yields which comprises preparing a solution containing cardanol and diamylamine in a ratio of one mole of cardanol to at least one mole of said amine, adding to said solution an amount of formaldehyde at least equal to a mole e lent of said cardanol to provide a formaldehyde-containing mixture, said solution being maintained at a temperature not e: ceeding about 20 C. until said formaldehyde addition is completed, heating the resulting formaldehyde-ccnt ining mixture to a temperature above 20 C. but below the boiling point of said mixture to expedite reaction thereof and convert the cardanol therein to diamylaminoriethylcardanol to provide a diamylaminomethylcaramylaininornethylcardanol from said mixture.

a dialiphaticaminoalkylcardanol-con-' 13. A method for preparing diamylaminomethylcardanol in high yields and in substantially pure form which comprises preparing a solution containing cardanol and diamylamine in the ratio or" one mole of cardanol to at least one mole of said amine, adding to said solution an amount of formaldehyde at least equal to a mole equivalent of said carclanol to provide a formaldehyde-containing mixture, said solution being maintained at a temperature not exceeding about 20 C, until said formaldehyde addition is completed, heatin the resulting formaldehydecontaining ixture to a temperature not exceeding the boiling point of said mixture to expedite reaction thereof and convert the cardanol to diamyla i lcardanol to provide a mixture conta diainylarninomethyicardanol, subjecting said diamyl ninomethyicardanol-containing mixture to distillation at a temperature sufficient to remove unreacted diamylarnine and formaldehyde and by roducts contained in said mixture but at a temperature below that at which diamylamin'ometi yicardanol tends to decompose, and recovering diamyiaminomethylcardanol in subpure form as the residue of said distillation.

inetn as defined in claim 13, wherein the diamyla omethylcardanol-containing mixture is subjected to distillation at below about 153 G.

ANTHONY J. REVUKAS.

REFERENCES CITED The following references are of record in the file of this patent:

UNXTED STATES PATENTS Number Name Date 1,821,095 Harvey Sept. 1, 1931- l,838,070 Harvey Dec. 22, 1931 1,833,077 Harvey Dec. 22, 1931 1,921,292 Harvey Aug. 8, 1933' 2,335,503 Novotny et a1 Nov. 30, 1943 2,363,13 l lvi'cCleary Nov. 21, 1944 FOREIGN PATENTS Number Country Date 635,578 France Mar. 19, 1928 2.725%?) Great Britain Oct. 8, 1928 OTHER REFERENCE Harvey et al.: Ind. Eng. Chem, vol. 32, pp. 1306-1310 (19%). 

